China Petroleum Processing and Petrochemical Technology Scientific Research 2011,Vol. 13, No.

2, pp 9-13 June 30, 2011

Laboratory Research on Tahe AR Fluid Coking on Weak Acid Catalysts

Wu Zhiguo; Li Yanjun; Shen Haiping
(SINOPEC Research Institute of Petroleum Processing, Beijing 100083)
Abstract: Fluid coking on micro-spherical particles with acid sites on them could produce more light oils from Tahe AR. The conversion rate could increase by about 20% on the catalyst B compared to that obtained on the catalyst A and the light oil yield could increase by about 12%. The yield of gasoline and diesel was more than 50% from Tahe AR over the catalyst B. Tests on acidity of the catalyst B by pyridine FT-IR spectrometry showed that the total acid content and the ratio of weak acid number to total acid number were higher than other catalysts. Key words: fluid coking; weak acid catalyst; fixed fluidized bed; Tahe AR

1Introduction
The non-renewable energy resources especially crude oils are depleting with time. Crude oils processed at refineries are getting heavier and heavier. Efficient oil refining aimed at producing more fuel oils from residuum is the foremost concern of refiners at present and in the future. Delayed coking and fluid coking are both thermal cracking processes. Their products selectivity is poorer than catalytic cracking. The reactions of fluid coking mainly take place on inert micro-particles. Saturated paraffins can crack to form lower molecular olefins and paraffins. Side chains are detached from molecules of aromatics, naphthenes and polynuclear aromatics. Naphthenes can be dehydrogenated to form aromatics, and small ring aromatics can condense into polynuclear aromatics. Eventually, 20%35% of coke can be formed on microparticles, whereas the gas and liquid oil products after exiting the fluidized bed reactor are separated into various products. Suppose there are some acid sites existing on the microparticles, the reactions taking place on them will be catalyzed by the acid sites, and the product selectivity may be improved. Fluid coking processes can treat residual oils. The molecules of feed oils are very large. Their dynamic diameters are between 2.5 nm and 15 nm[1]. Weak acid sites are suitable for catalytic cracking of heavy feed oils . Strong
[2]

acids would bring about more coke causing quick deactivation of catalysts[3].

2Experimental
2.1Catalysts preparation
The raw materials for preparation of catalysts were kaolinite, pseudoboehmite, aluminum sol, ZSM-5 zeolite, and deionized water. The materials were mixed together according to the designed prescription, and the slurry formed thereby was fully stirred, and was then spraydried to form microspherical particles. The mean diameter of the microparticles is about 71 m. The microparticles labeled as the catalyst samples (A, B, C, and D, as showed in Table 1) were calcined at 900 for 2 hours. The catalyst samples C and D contain about 18% of rare earth oxides, while the catalyst sample D also contains about 10% of the ZSM-5 zeolite. The composition of catalyst samples are listed in Table 1.

2.2XRD Analysis
The anode material of XRD analysis apparatus was Cu. The ratio of K2/K1 was 0.5. The data angle ranged from 4.02503 to 79.96726. The scan was conducted continuously on every 0.5.
Corrresponding Author: Dr. Wu Zhiguo, Telephone: +86-1082368265; E-mail: wuzhiguo.ripp@sinopec.com

China Petroleum Processing and Petrochemical Technology Table 1The composition of catalyst samples
Mass fraction, % Items Catalyst A 0.07 0.10 Base +16.00 3.50 0.17 0.47 0.12 0.35 0.62 0 Catalyst B 0.04 0.12 +15.00 +1.00 4.20 0.14 0.46 0.12 0.37 0.65 0 Catalyst C 0.09 0.13 +1.00 Base 0.12 0.20 0.33 0.42 0.24 0.63 18.74 Catalyst D 0.09 0.10 -8.00 +10.00 0.53 0.22 0.32 0.35 0.24 0.55 17.80

2011,13(2):9-13 Table 2Property of feed oil

Items Density(20 ), g/cm3 Kinematic viscosity, mm2/s At 80 At 100 Flash point (open cup), Freezing point, Carbon residue(w), % Ash(w),% Hydrocarbon group analysis, m% Saturated hydrocarbons Aromatics Resins Asphaltenes Elemental analysis(w), % C H S N Metal analysis, wppm Fe Ni V Simulated distillation, Initial boiling point 5% 10% 30% 50% 70% 258 321 361 468 570 62263% 38.2 30.9 223 ASTM D6352 85.68 10.64 2.5 0.35 SH/T 0656 SH/T 0656 GB/T 17040 Chemiluminescence RIPP 124-90 29.0 32.5 23.8 14.7 867.0 252.9 170 12 16.8 0.058 GB/T 3536 GB/T 510 GB/T 17144 GB/T 508 RIPP 10-90 Tahe AR 0.9908 Method of analysis GB/T 2540 GB/T 11137

Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 Fe2O3 Re2O3

2.3Catalyst acidity analysis

The catalyst acidity was analyzed by FT-IR spectroscopy. The probe molecule was pyridine, which could be adsorbed on both Brnsted and Lewis acid sites because of its alkalinity. The catalyst sample was degassed under vacuum at about 350 prior to pyridine adsorption. After pyridine was adsorbed to saturation, the sample was heated to 200 under vacuum at a pressure of 10-3 Pa for 30 min. After the sample was cooled down at 10-3 Pa, it was placed in the sample compartment for transmission scanning with infrared ray. Then desorption was carried again at 350 under vacuum and the sample was scanned after it cooled down. The test data obtained upon desorption at 200 were counted as total amount of acids and the data obtained upon desorption at 350 were calculated as the total amount of strong acids. Their difference is the amount of weak acids. The typical peak of FT-IR spectroscopy at about 1 450 cm-1 is ascribed to the Lewis acid and the peak near 1 540 cm-1the Brnsted acid.

2.5Fluid coking equipment

The fluid coking test equipment is shown in Figure 1. The catalyst inventory in the fixed fluidized bed reactor is about 200 g. Feed oil was heated and pumped into the reactor. The feed oil was weighed by an electronic balance. Oil products were collected in the bottle 19 and gas was collected in the collector 13. The samples were taken and analyzed by chromatography. The coked catalyst reacted upon oxygen to form flue gas containing CO2, steam and CO. Steam was cooled down into water and collected in the bottle 15. CO was transformed to CO2 in furnace 16 and all CO2 gas was analyzed by the infrared instrument 17, which gave the data on coke formation.

2.4Feed oil for fluid coking test

The feed oil is an atmospheric residue of Tahe crude oil (Tahe AR). Its property is listed in Table 2. The initial boiling point of Tahe AR is about 258 , and its hydrogen content is around 10.64%.

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Wu Zhiguo, et al. Laboratory Research on Tahe AR Fluid Coking on Weak Acid Catalysts

would lead to more coke formation and make catalyst deactivated quickly. The catalyst acidity is depicted in Table 3. Since the catalyst samples were treated under high temperature, there were no Brnsted acids detected by pyridine FT-IR spectroscopy. The acid data in Table 3 are associated with the Lewis acids and are calculated based on the peak area of FT-IR spectra.
Figure 1Fluid coking equipment
1Pressurized air; 2Oxygen; 3Electronic balance; 4Feed oil pump; 5Deionized water; 6Water pump; 7 & 8Furnace; 9Reactor; 10Preheater; 11 & 12Cooler; 13Gas collector; 14Salted water; 15Water collector; 16CO converter; 17Infrared instrument; 18 &20Vent; 19Product oil collector Catalyst sample A B C D

Table 3Catalyst acidity data

Total acids 18.4 85.0 78.5 63.3 Weak acids 8.5 38.6 32.0 28.5 Strong acids 9.9 46.4 46.5 34.8

3Results and Discussion

3.1XRD patterns
The XRD patterns of four catalyst samples are presented in Figure 2. The typical peaks of the samples are notable. The catalyst A contains the highest SiO2, so the peak of SiO2 near 20 is the largest[4]. The Al2O3 content in the catalyst B is higher than other samples, and its typical peak between 65and 70 has a higher value. The peak near 30 indicates the presence of rare earth oxides, which exist in the catalysts C and D. The catalyst D has different XRD pattern because it contains about 10% ZSM-5 zeolite.

The catalyst A has the lowest acid amount. The catalyst B and the catalyst C have nearly the same strong acid amount, but the former has a larger weak acid amount. The catalysts A, B and C are non-zeolite based catalysts, so their acidity originates from different sources as compared with the catalyst D. The acidity of catalyst D is ascribed to its ZSM-5 content which has a typical crystal structure, while the acidity of catalysts A, B and C originates from their amorphous silicon and aluminum structure.

3.3nfluence of catalysts on fluid coking I products

The Tahe AR was pumped and sprayed into a fixed fluidized bed operating at a temperature of 500 . By maintaining the ratio of catalyst to oil (C/O) at 7 and the weight hourly space velocity at 4 h-1, the four catalyst samples with different characteristics were tested on the product yields, respectively. The test results are listed in Table 4.
Table 4Products distribution from Tahe AR
Items Products distribution, % Dry gas 2.53 4.27 14.35 24.73 40.44 13.68 100 59.56 3.23 9.37 25.53 27.43 14.68 19.76 100 85.31 3.29 8.00 15.30 24.85 27.05 21.51 100 72.95 4.11 15.05 9.37 21.28 30.40 19.79 100 69.60 A B C D

Figure 2XRD patterns of catalyst samples A; B; C; D

LPG Gasoline Diesel >350 Coke Total yield Conversion, %

3.2Catalyst acidity
The acid sites on the catalyst surface or inside the catalyst are critical for hydrocarbons cracking. The weak acids are suitable for cracking of large molecules. The strong acids

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China Petroleum Processing and Petrochemical Technology

2011,13(2):9-13

Under the same reaction condition, the catalyst B demonstrated a highest conversion rate, followed by the catalyst C, while catalysts D and A ranked the third and the fourth in terms of the conversion rate, respectively. This catalytic performance order in terms of the conversion rate is similar to the order according to the content of total acids and weak acids in the catalyst. The conversion rate was high but the coke yield was low for the catalyst B, which might be attributed to the reasonable weak acid content in catalyst B (with the ratio of weak acids/total acids equating to 41.9%). The strong acid ratio (strong acids/total acids) was about 59.24% for the catalyst C, which was the highest among 4 catalysts, so its coke yield was the highest. Thanks to the function of shape selectivity of the ZSM-5 zeolite, the liquefied petroleum gas yield was high and the gasoline yield was low for the catalyst D. The selective cracking performance of the ZSM-5 zeolite made gasoline fraction partially cracked to lighter hydrocarbons, especially propylene. It can be seen from the data listed in Table 5 that the propylene content was by about 10% higher than that provided by other catalyst samples.
Table 5Composition of gas products
Items Dry gas, % Hydrogen Methane Ethylene Ethane LPG, % Propylene Propane Butene n-Butane Isobutane Total, % A 37.28 1.73 16.95 6.72 11.88 62.72 22.70 6.86 27.03 2.79 3.34 100 B 25.65 1.43 12.22 4.39 7.60 74.36 24.84 5.18 33.52 2.62 8.20 100 C 29.56 1.73 14.32 4.59 8.92 70.44 27.13 6.07 32.23 2.86 2.15 100 D 21.44 0.96 7.61 8.11 4.76 78.56 39.66 4.86 29.40 2.07 2.57 100

sites would be separated farther, and the opportunity for occurrence of hydrogen transfer reactions would be less, so the olefin content in products would be higher. If the acid site density is higher, the hydrogen transfer reactions would take place more frequently, and the olefin content in products would be lower, while the alkane and aromatics content would be higher. The outcome of these reactions can be verified by the data listed in Table 5 and Table 6. The acid site density of catalyst B is higher than others, so its olefin content is lower in gasoline, and the contents of aklanes and aromatics are higher than those achieved by other non-zeolite catalysts.
Table 6The PIONA data of gasoline
Items n-Alkanes Isoalkanes Olefins Naphthenes Aromatics A 6.63 16.33 45.2 6.83 25.01 B 5.52 19.19 41.19 6.65 27.45 C 7.52 14.69 45.25 6.11 26.43 D 9.21 12.61 43.91 4.72 29.55

w,%

4Conclusions
The conversion of Tahe AR on amorphous silicon and aluminum catalyst with higher aluminum content during fluid coking could reach about 85.31%, and its light oil yield was more than 50%, which might be attributed to the reasonable acid content and acidity distribution. Addition of ZSM-5 zeolite to the catalyst composition could enhance selective cracking of gasoline to propylene thanks to its unique crystal structure.

[1] Zhu Huyuan, He Mingyuan, Song Jiaqing. Resid cracking and bulky molecule cracking abilities of RFCC catalysts[J]. Petroleum Refinery Engineering, 2000, 30(8): 47-51(in Chinese) Maglio A, Keweshan C F, Madon R J, et al. Advanced FCC [2] catalyst matrix technology for reduced coke and slurry yields[C]. NPRA Annual Meeting, AM-94-59. San Antonio, Texas, 1994-03-20 Silverman L D, Winkler S, Tiethof J A, et al. Matrix effects [3] in catalytic cracking[C]. NPRA Annual Meeting, AM-8662. Los Angeles, California, 1986-03-23

References

The acid site density is related to the hydrogen transfer reactions as shown below[5]: Olefin + Naphthene Alkane + Aromatics Olefin + Olefin Aromatics + H2 Olefin + Olefin Alkane + Diolefin If the acid site density is lower, the distance between two

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Wu Zhiguo, et al. Laboratory Research on Tahe AR Fluid Coking on Weak Acid Catalysts [4] Han Jingxiang, She Lijuan, Zhai Lixin, et al. Preparation of nanometer SiO2 by chemical precipitation[J]. Bulletin of the Chinese Ceramic Society, 2010, 29(3): 681-685(in Chinese) Saeed Alerasool. Matrix acidity determination: a bench [5] scale method for predicting resid cracking of FCC catalysts[J]. Ind Eng Chem Res, 1995, 34: 434-439

Startup of First in China Commercial Demonstration Unit for Manufacture of Synthetic Natural Gas from Coke-oven Gas
The first in China commercial demonstration unit for methanation of coke-oven gas a 50 thousand m3/day synthetic natural gas from coke-oven gas independently developed by the Southwest Chemical Research and Design Institute will be put on stream at the Shanxi Xinloujing Energy Company by the end of 2011. This project not only can completely realize zero discharge of cokeoven gas, but also can reduce emission of 338 thousand tons of CO2, with the investment cost equating to mere 30%40% of total cost for manufacturing natural gas from coal. Coke-oven gas is a toxic and inflammable by-product gas formed in the course of high-temperature dry distillation of coal in coke oven along with the production of coke and coal tar products. Previous research has proposed a variety of methods for utilization of coke-oven gas, including direct combustion, power generation, production of urea, manufacture of methanol, manufacture of natural gas, and steelmaking. The technical analysis study shows that manufacture of natural gas from coke-oven gas can result in the best economic benefits, and the total capital investment can be paid back in 34 years. The production of compressed natural gas via methanation of coke-oven gas obtained from an 1.0 Mt/a coking unit can amount to 100 million m3 a year. The proprietary technology for manufacture of synthetic natural gas from coke-oven gas developed by the Southwest Chemical Research and Design Institute is a key project of the Science and Technology Support Program envisaged in the National Eleventh Five-Year Plan, and had passed in January 2011 the experts acceptance tests sponsored by the Ministry of Science and Technology of China. Currently the Southwest Chemical Research and Design Institute has signed technical license contracts with two enterprises in Shanxi province after having submitting the project feasibility reports for more than twenty enterprises. The specific features of this novel technology include: a catalyst capable of simultaneously performing the function of methanation, oxygen removal and conversion of higher hydrocarbons; a methanation process scheme covering multiple-stage of serial connection, gas recycle, and steam recovery; reasonable removal of methanation heat for decent utilization; integration and innovation of technologies for coke-oven gas cleanup and methanation, and separation of PSA gas to produce a 99.99%-purity hydrogen along with manufacture of synthetic natural gas.

Technical Appraisal of Project Development and Commercial Application of Catalyst for Hydrotreating of Isophthalic Acid
The project Development and commercial application of catalyst for hydrotreating of isophthalic acid (PIA) jointly undertaken by the SINOPEC Shanghai Petrochemical Research Institute (SPRI) and the SINOPEC Yanshan Branch Company has recently passed the technical appraisal sponsored by the SINOPEC Science and Technology Development Division. The CIP-2010 type catalyst for hydrotreating PIA developed by SPRI, characterized by low content of noble metals, high dispersiveness and high metal loading, has been operating successfully in the 60-kt/a PIA unit for more than one year, with the content of 3-CBA in PIA product meeting the requirements for excellent quality product. During this period of time the catalyst did not need caustic washing, and the process unit ran smoothly. According to the comments of experts attending the appraisal meeting, the technology for manufacture of the CIP-2010 type catalyst is innovative, and the catalyst has high activity and good selectivity, with its comprehensive performance reaching the internationally advanced level.

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